WO2012176669A1 - Separator having heat resistant insulation layers - Google Patents
Separator having heat resistant insulation layers Download PDFInfo
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- WO2012176669A1 WO2012176669A1 PCT/JP2012/065100 JP2012065100W WO2012176669A1 WO 2012176669 A1 WO2012176669 A1 WO 2012176669A1 JP 2012065100 W JP2012065100 W JP 2012065100W WO 2012176669 A1 WO2012176669 A1 WO 2012176669A1
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- heat
- separator
- resistant insulating
- insulating layer
- battery
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/411—Organic material
- H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/411—Organic material
- H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
- H01M50/417—Polyolefins
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/411—Organic material
- H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
- H01M50/423—Polyamide resins
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/431—Inorganic material
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/443—Particulate material
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/446—Composite material consisting of a mixture of organic and inorganic materials
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
- H01M50/451—Separators, membranes or diaphragms characterised by the material having a layered structure comprising layers of only organic material and layers containing inorganic material
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
- H01M50/457—Separators, membranes or diaphragms characterised by the material having a layered structure comprising three or more layers
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
- H01M50/491—Porosity
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2220/00—Batteries for particular applications
- H01M2220/20—Batteries in motive systems, e.g. vehicle, ship, plane
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y02T10/00—Road transport of goods or passengers
- Y02T10/60—Other road transportation technologies with climate change mitigation effect
- Y02T10/70—Energy storage systems for electromobility, e.g. batteries
Definitions
- the present invention relates to a separator with a heat-resistant insulating layer.
- lithium ion secondary batteries are considered suitable for electric vehicles because of their high energy density and high durability against repeated charge and discharge, and there is a tendency for higher capacity to be further developed. Therefore, ensuring the safety of lithium ion secondary batteries has become increasingly important.
- a lithium ion secondary battery generally includes a positive electrode in which a positive electrode active material or the like is applied to both surfaces of a positive electrode current collector, and a negative electrode in which a negative electrode active material or the like is applied to both surfaces of the negative electrode current collector. And the said positive electrode and a negative electrode are connected through the electrolyte layer which hold
- a polyolefin microporous film having a thickness of about 20 to 30 ⁇ m is often used.
- a microporous polyolefin membrane may cause thermal shrinkage due to temperature rise in the battery and a short circuit associated therewith.
- Patent Document 1 describes that such a separator is used for a wound lithium ion battery, and thermal contraction due to temperature rise in the battery is suppressed.
- the present invention has been made in view of such problems of the conventional technology. And the objective is to provide the separator with a heat resistant insulating layer which can suppress the generation
- a separator with a heat-resistant insulating layer includes a resin porous substrate and a heat-resistant insulating layer formed on both surfaces of the resin porous substrate and containing heat-resistant particles having a melting point or a heat softening point of 150 ° C. or higher.
- the parameter X represented by Equation 1 is 0.15 or more:
- a ′ and A ′′ are the thicknesses ( ⁇ m) of the respective heat-resistant insulating layers formed on both surfaces of the porous resin substrate, where A ′ ⁇ A ′′, and C is the value of the separator with the heat-resistant insulating layer.
- FIG. 1 is a cross-sectional view schematically showing a flat plate type non-bipolar lithium ion secondary battery according to an embodiment of the present invention.
- FIG. 2 is a schematic view showing an outline of a separator with a heat-resistant insulating layer in one embodiment of the present invention.
- FIG. 3 is a cross-sectional view schematically showing a separator with a heat-resistant insulating layer in one embodiment of the present invention.
- FIG. 4 is a perspective view schematically showing the appearance of a flat plate type non-bipolar lithium ion secondary battery according to an embodiment of the present invention.
- FIG. 5 is a schematic diagram for explaining a curl height measuring method in the embodiment.
- FIG. 1 is a cross-sectional view schematically showing a flat plate type non-bipolar lithium ion secondary battery according to an embodiment of the present invention.
- FIG. 2 is a schematic view showing an outline of a separator with a heat-resistant insulating layer in one embodiment of the present invention.
- FIG. 6 is a graph showing the relationship between the value of parameter X and the curl height in the separators produced in the examples and comparative examples.
- FIG. 7 is a graph showing the relationship between the value of parameter Y, curl height, and battery rate characteristics in the separators produced in the examples and comparative examples.
- an electric device using the separator with a heat-resistant insulating layer of the present embodiment is excellent as a driving power source or an auxiliary power source for a vehicle.
- the electrical device of the present embodiment is not particularly limited as long as it uses a separator with a heat resistant insulating layer described below.
- a lithium ion battery will be described as an example of the electric device.
- a lithium ion battery As a usage form of a lithium ion battery, it may be used for either a lithium ion primary battery or a lithium ion secondary battery. Since it is preferably excellent in high cycle durability, it is desirable to use it as a lithium ion secondary battery for a vehicle driving power source or for portable devices such as a mobile phone.
- the separator with a heat-resistant insulating layer can be applied to a flat plate type (flat type) battery.
- a flat plate type battery structure By adopting a flat plate type battery structure, long-term reliability can be secured by a sealing technique such as simple thermocompression bonding, which is advantageous in terms of cost and workability.
- the separator with a heat-resistant insulating layer can be applied to a solution electrolyte type battery using a solution electrolyte such as a non-aqueous electrolyte solution.
- the present invention can also be applied to an electrolyte layer such as a gel electrolyte type battery using a polymer gel electrolyte.
- FIG. 1 shows an overall structure of a flat plate type (flat type) lithium ion secondary battery according to an embodiment of the present invention. Note that a flat plate type lithium ion secondary battery is also simply referred to as a “stacked battery”.
- the stacked battery 10 of the present embodiment has a structure in which a substantially rectangular power generation element 21 in which a charge / discharge reaction proceeds is sealed inside a battery exterior material 29.
- the power generation element 21 has a configuration in which a positive electrode, an electrolyte layer 17, and a negative electrode are stacked.
- the positive electrode has a configuration in which positive electrode active material layers 13 are disposed on both surfaces of the positive electrode current collector 11.
- the electrolyte layer 17 has a configuration in which an electrolyte (electrolytic solution or electrolyte gel) is held in a separator.
- the negative electrode has a configuration in which the negative electrode active material layers 15 are disposed on both surfaces of the negative electrode current collector 12. In other words, the negative electrode, the electrolyte layer, and the positive electrode are laminated in this order so that one positive electrode active material layer 13 and the negative electrode active material layer 15 adjacent thereto face each other with the electrolyte layer 17 therebetween. ing.
- the adjacent positive electrode, electrolyte layer, and negative electrode constitute one unit cell layer 19. Therefore, it can be said that the stacked battery 10 shown in FIG. 1 has a configuration in which a plurality of single battery layers 19 are stacked and electrically connected in parallel.
- the positive electrode current collector 13 located on both outermost layers of the power generation element 21 is provided with the positive electrode active material layer 13 on only one side, but the positive electrode active material layer may be provided on both sides. That is, instead of using the current collector exclusively for the outermost layer provided with the positive electrode active material layer only on one side, a current collector having the positive electrode active material layer on both sides may be used as it is as the current collector for the outermost layer.
- the arrangement of the positive electrode and the negative electrode is reversed from that in FIG. 1 so that the negative electrode current collector is positioned on both outermost layers of the power generation element 21, and the negative electrode active material is disposed on one or both surfaces of the outermost negative electrode current collector.
- a material layer may be arranged.
- the positive electrode current collector 11 and the negative electrode current collector 12 are respectively attached with a positive electrode current collector plate 25 and a negative electrode current collector plate 27 that are electrically connected to the respective electrodes (positive electrode and negative electrode).
- the positive electrode current collecting plate 25 and the negative electrode current collecting plate 27 are led out of the battery outer packaging material 29 so as to be sandwiched between the end portions of the battery outer packaging material 29.
- the positive electrode current collector plate 25 and the negative electrode current collector plate 27 are ultrasonically welded to the positive electrode current collector 11 and the negative electrode current collector 12 of each electrode via a positive electrode lead and a negative electrode lead (not shown), respectively, as necessary. Or resistance welding or the like.
- the lithium ion secondary battery described above is characterized by a separator.
- main components of the battery including the separator will be described.
- the positive electrode active material layer 13 and the negative electrode active material layer 15 contain an active material, and further contain other additives as necessary.
- the positive electrode active material layer 13 includes a positive electrode active material.
- a positive electrode active material for example, LiMn 2 O 4 , LiCoO 2 , LiNiO 2 , Li (Ni—Co—Mn) O 2, and lithium—such as those in which some of these transition metals are substituted with other elements
- examples thereof include transition metal composite oxides; lithium-transition metal phosphate compounds; lithium-transition metal sulfate compounds.
- two or more positive electrode active materials may be used in combination.
- a lithium-transition metal composite oxide is used as the positive electrode active material.
- a positive electrode active material other than the above may be used.
- the negative electrode active material layer 15 includes a negative electrode active material.
- the negative electrode active material include carbon materials such as graphite (graphite), soft carbon, and hard carbon; lithium-transition metal composite oxides (for example, Li 4 Ti 5 O 12 ); metal materials; lithium alloy negative electrode materials, and the like. Is mentioned.
- two or more negative electrode active materials may be used in combination.
- a carbon material or a lithium-transition metal composite oxide is used as the negative electrode active material. Note that negative electrode active materials other than those described above may be used.
- the average particle diameter of each of the active materials contained in the positive electrode active material layer 13 and the negative electrode active material layer 15 is not particularly limited, but is preferably 1 to 100 ⁇ m, more preferably 1 to 20 ⁇ m from the viewpoint of high output. .
- the positive electrode active material layer 13 and the negative electrode active material layer 15 preferably contain a binder.
- the binder used for the positive electrode active material layer 13 and the negative electrode active material layer 15 is not particularly limited.
- the binder include polyethylene, polypropylene, polyethylene terephthalate (PET), polyether nitrile, polyacrylonitrile, polyimide, polyamide, cellulose, carboxymethyl cellulose (CMC), ethylene-vinyl acetate copolymer, polyvinyl chloride, styrene / butadiene.
- SBR Rubber
- isoprene rubber butadiene rubber, ethylene / propylene rubber, ethylene / propylene / diene copolymer, styrene / butadiene / styrene block copolymer and hydrogenated product thereof, styrene / isoprene / styrene block copolymer and Examples thereof include thermoplastic polymers such as hydrogenated products.
- PVdF polyvinylidene fluoride
- PTFE polytetrafluoroethylene
- FEP tetrafluoroethylene / hexafluoropropylene copolymer
- PFA tetrafluoroethylene / perfluoroalkyl vinyl ether copolymer
- fluororesins such as ethylene / tetrafluoroethylene copolymer (ETFE), polychlorotrifluoroethylene (PCTFE), ethylene / chlorotrifluoroethylene copolymer (ECTFE), and polyvinyl fluoride (PVF).
- vinylidene fluoride-hexafluoropropylene fluorororubber VDF-HFP fluororubber
- vinylidene fluoride-hexafluoropropylene-tetrafluoroethylene fluororubber VDF-HFP-TFE fluororubber
- Vinylidene fluoride-pentafluoropropylene fluorine rubber VDF-PFP fluorine rubber
- vinylidene fluoride-pentafluoropropylene-tetrafluoroethylene fluorine rubber VDF-PFP-TFE fluorine rubber
- vinylidene fluoride-perfluoro Methyl vinyl ether-tetrafluoroethylene fluorine rubber VDF-PFMVE-TFE fluorine rubber
- vinylidene fluoride-chlorotrifluoroethylene fluorine rubber VDF- TFE-based vinylidene fluorine rubber
- an epoxy resin etc. are mentioned as a binder.
- polyvinylidene fluoride, polyimide, styrene / butadiene rubber, carboxymethyl cellulose, polypropylene, polytetrafluoroethylene, polyacrylonitrile, and polyamide are more preferable.
- These binders are preferably used for the active material layer because they are excellent in heat resistance, have a very wide potential window, and are stable at both the positive electrode potential and the negative electrode potential. These binders may be used alone or in combination of two or more.
- the amount of the binder contained in the active material layer is not particularly limited as long as the amount can bind the active material.
- the amount of the binder is preferably 0.5 to 15% by mass, more preferably 1 to 10% by mass with respect to the active material layer.
- Examples of other additives contained in the active material layer include a conductive additive, an electrolyte salt, and an ion conductive polymer.
- the conductive assistant means an additive blended to improve the conductivity of the positive electrode active material layer or the negative electrode active material layer.
- the conductive auxiliary agent include carbon materials such as carbon black such as acetylene black, graphite, and carbon fiber.
- electrolyte salt examples include Li (C 2 F 5 SO 2 ) 2 N, LiPF 6 , LiBF 4 , LiClO 4 , LiAsF 6 , LiCF 3 SO 3 and the like.
- Examples of the ion conductive polymer include polyethylene oxide (PEO) and polypropylene oxide (PPO) polymers.
- the compounding ratio of the components contained in the positive electrode active material layer and the negative electrode active material layer is not particularly limited.
- the blending ratio can be adjusted by appropriately referring to known knowledge about the nonaqueous electrolyte secondary battery.
- the thickness of each active material layer is not particularly limited, and conventionally known knowledge about the battery is referred to as appropriate. As an example, the thickness of each active material layer is about 2 to 100 ⁇ m.
- the positive electrode current collector 11 and the negative electrode current collector 12 are made of a conductive material.
- the size of the current collector is determined according to the intended use of the battery. For example, in the case of a large battery that requires high energy density, a current collector having a large area is used.
- the lithium ion battery of the present embodiment is preferably a large battery, and the size of the current collector used is, for example, a long side of 100 mm or more, preferably 100 mm ⁇ 100 mm or more, more preferably 200 mm ⁇ It is 200 mm or more.
- the thickness of the current collector is usually about 1 to 100 ⁇ m.
- the shape of the current collector is not particularly limited. In the laminated battery 10 shown in FIG. 1, in addition to the current collector foil, a mesh shape (such as an expanded grid) can be used.
- metal is preferably used. Specific examples include aluminum, nickel, iron, stainless steel, titanium, and copper. In addition to these, a clad material of nickel and aluminum, a clad material of copper and aluminum, or a plating material of a combination of these metals is preferably used. Moreover, the foil by which aluminum is coat
- the electrolyte layer 17 has a configuration in which an electrolyte is held at the center in the surface direction of the separator of the present embodiment.
- the separator with a heat-resistant insulating layer in the present embodiment includes a resin porous substrate and a heat-resistant insulating layer containing heat-resistant particles having a melting point or a heat softening point of 150 ° C. or higher formed on both surfaces of the resin porous substrate. Further, the separator is characterized in that a parameter X represented by the following mathematical formula (1) is 0.15 or more.
- a ′ and A ′′ indicate the thickness ( ⁇ m) of each heat-resistant insulating layer formed on both surfaces of the porous resin substrate, where A ′ ⁇ A ′′.
- C represents the total thickness ( ⁇ m) of the separator with a heat-resistant insulating layer.
- the separator of the present embodiment it is possible to suppress the warpage of the end portion and the occurrence of curling. Therefore, when the separator of the present embodiment is used, the yield can be improved in the manufacturing process of the flat plate type battery.
- the value of the parameter X is less than 0.15, curl cannot be ignored, and particularly when a large flat-plate laminated battery is manufactured, the yield is remarkably lowered.
- the separator is piled up. Then, the turned portion is stepped on, and the curled and turned portion is folded and laminated. In such a case, since the cell is short-circuited, the yield is greatly reduced and the cost is increased.
- the separator 1 with a heat-resistant insulating layer of the present embodiment has a structure in which the heat-resistant insulating layers 3 are provided on both surfaces of the resin porous substrate 2 as shown in FIG.
- the cause of the curling of the separator is that the thermal stress remains when the heat-resistant insulating layer is applied to the resin porous substrate and is heated and dried by hot air drying or the like. Specifically, since the resin contained in the resin porous substrate has a large coefficient of linear expansion when heated, the resin porous substrate becomes stretched when heated and dried. On the other hand, since the heat-resistant insulating layer is formed using heat-resistant particles having a melting point or a heat softening point of 150 ° C. or higher, the linear expansion coefficient is sufficiently small in the temperature range of heat drying and hardly expands.
- the resin porous substrate contracts greatly, but the heat-resistant insulating layer hardly contracts.
- the resin porous substrate wants to shrink, and the heat-resistant insulating layer resists the curling in such a manner that the resin porous substrate is wound inside. Will occur.
- the heat-resistant insulating layer 3 is applied to both surfaces of the resin porous substrate 2 so that the thicknesses A ′ and A ′′ of the heat-resistant insulating layer 3 are as identical as possible.
- the balance of shrinkage stress of the heat-resistant insulating layer 3 in the vertical direction can be improved and curling can be suppressed.
- the thicknesses A ′ and A ′′ of the heat-resistant insulating layer 3 with respect to the total thickness C of the separator are controlled to a specific relationship. ing.
- the parameter X in the above formula (1) is set to 0.15 or more. Thereby, it becomes difficult to produce a big curl, and the problem of folding and curling during the stacking operation can be solved.
- the parameter X represented by the mathematical formula (1) is an index as to whether or not a difference in shrinkage stress due to drying of the heat-resistant insulating layers formed on both surfaces of the resin porous substrate becomes obvious. This means that the difference in shrinkage stress of the heat-resistant insulating layer becomes obvious.
- the influence of the difference in shrinkage stress between the heat-resistant insulating layers on both sides is large with respect to the internal stress of the resin porous substrate, curling is likely to occur.
- the smaller the thickness A ′, A ′′ of the heat-resistant insulating layer compared to the total thickness C of the separator the smaller the value of the parameter X.
- the value of the parameter X is 0.15 or more, preferably 0.20 or more.
- the value of X is less than 0.15, the effect of curl cannot be ignored, and the yield is significantly reduced in the production of large flat-plate laminated batteries.
- the upper limit of the parameter X represented by the above mathematical formula (1) is not particularly limited as long as curling of the separator can be suppressed, but can be set to 1.0, for example.
- the parameter Y represented by the following mathematical formula (2) is preferably in the range of 0.3 to 0.7.
- X is as defined above, and D is the porosity (%) of the heat-resistant insulating layer 3.
- the thickness (A ′, A ′′) of the heat-resistant insulating layer is increased, the value of X increases, but the ion permeability decreases and the rate characteristics decrease.
- the porosity of the heat-resistant insulating layer dominates the rate characteristics
- the two heat-resistant insulating layers are formed on both sides of the porous resin substrate with appropriate pressing force from both sides. If the holding force is too weak or biased, curling is likely to occur, and if the holding force is too strong, the ion permeability decreases and the rate characteristics of the battery decrease. there is a possibility.
- the parameter Y expressed by the above mathematical formula (2) is an index of how strong and even the two heat-resistant insulating layers hold both sides of the resin porous substrate. For example, if the pressing force is biased on both surfaces of the porous resin substrate due to the difference in the basis weight between the heat-resistant insulating layers on both surfaces, the value of Y is small. Further, the value of Y is small even when the heat-resistant insulating layer is thin or has a large porosity and therefore the pressing force of the heat-resistant insulating layer is weak. Furthermore, the larger the total thickness C of the separator, the smaller the value of Y.
- the value of the parameter Y is preferably 0.3 to 0.7, and more preferably 0.35 to 0.65. If the value of Y is 0.3 or more, curling is unlikely to occur. If the value of Y is 0.7 or less, high rate characteristics can be obtained.
- values measured using a micro gauge can be used as the thicknesses A ′ and A ′′ of the heat-resistant insulating layer and the total thickness C of the separator.
- the porosity D (%) of the layer is the mass Wi (g / cm 2 ) of the component i per unit area, the density di (g / cm 3 ) of the component i, and the heat resistance for each component i constituting the heat-resistant insulating layer.
- the thickness t (cm) of the insulating layer it can be obtained from the following formula (3): When the porosity of the heat-resistant insulating layers on both sides is different, the average value of these is calculated as the porosity D (% ) Value.
- the heat-resistant insulating layer 3 is provided on both sides of the resin porous substrate 2 in the stacking direction, that is, the direction in which the positive electrode, the negative electrode, and the electrolyte layer 17 are stacked. Moreover, it is preferable that the heat-resistant insulating layers 3 formed on both surfaces of the resin porous substrate 2 are directly laminated on the opposing surfaces of the heat-resistant insulating layers as shown in FIG. Furthermore, it is preferable that the heat-resistant insulating layer 3 is formed on both surfaces of the resin porous substrate 2. As shown in FIG. 3, the heat-resistant insulating layer 3 may be a single layer or a plurality of layers. Further, when the heat-resistant insulating layer 3 is composed of a plurality of layers, they may be formed of different materials.
- the resin porous substrate 2 examples include a porous sheet, a woven fabric, or a nonwoven fabric containing an organic resin that absorbs and holds an electrolyte.
- the organic resin contained in the resin porous substrate it is preferable to use polyolefins such as polyethylene (PE) and polypropylene (PP); polyimides such as polyimide and aramid; and polyesters such as polyethylene terephthalate (PET).
- the average value of pore diameters (average pore diameter) of pores formed in the resin porous substrate is preferably 10 nm to 1 ⁇ m.
- the pore diameter formed in the resin porous substrate can be determined by, for example, a nitrogen gas adsorption method.
- the thickness of the porous resin substrate is preferably 1 ⁇ m to 200 ⁇ m. Further, the porosity of the resin porous substrate is desirably 20 to 90%.
- a porous sheet that can be used as a resin porous substrate is a microporous membrane composed of a microporous polymer.
- polymers include polyolefins such as polyethylene (PE) and polypropylene (PP); laminates having a three-layer structure of PP / PE / PP, polyimide, and aramid.
- PE polyethylene
- PP polypropylene
- laminates having a three-layer structure of PP / PE / PP, polyimide, and aramid are examples of such as polyimide
- aramid aramid
- a polyolefin-based microporous membrane is preferable because it has a property of being chemically stable with respect to an organic solvent and can reduce the reactivity with an electrolytic solution.
- the thickness of the porous sheet cannot be uniquely defined because it varies depending on the application. However, in the use of a secondary battery for driving a motor of a vehicle, it is desirable that the thickness is 4 to 60 ⁇ m in a single layer or multiple layers.
- the fine pore diameter of the porous sheet is usually about 10 nm, but is preferably 1 ⁇ m or less at maximum.
- the porosity of the porous sheet is preferably 20 to 80%.
- polyester such as polyethylene terephthalate (PET); polyolefin such as PP or PE; polyimide, aramid, or the like can be used.
- the bulk density of the woven fabric or the nonwoven fabric is not particularly limited as long as sufficient battery characteristics can be obtained by the impregnated electrolytic solution.
- the porosity of the woven or non-woven fabric is preferably 50 to 90%.
- the thickness of the woven or non-woven fabric is preferably 5 to 200 ⁇ m, particularly preferably 5 to 100 ⁇ m. If the thickness is 5 ⁇ m or more, the electrolyte retainability is good, and if it is 100 ⁇ m or less, the resistance is difficult to increase excessively.
- the method for preparing the resin porous substrate is not particularly limited.
- the resin porous substrate is a polyolefin-based microporous membrane
- the polyolefin is dissolved in a solvent and then extruded into a sheet, then the solvent is removed, and the resin porous substrate is prepared by a method of performing uniaxial stretching or biaxial stretching. Can do.
- a solvent paraffin, liquid paraffin, paraffin oil, tetralin, ethylene glycol, glycerin, decalin, etc. can be used as a solvent.
- Heat-resistant insulating layer (heat-resistant insulating porous layer)
- a material having a high heat resistance having a melting point or a heat softening point of 150 ° C. or higher, preferably 240 ° C. or higher is used as the material of the heat resistant particles constituting the heat resistant insulating layer.
- thermal softening point refers to a temperature at which a heated substance softens and begins to deform, and refers to a Vicat softening temperature.
- grain is not specifically limited, For example, it can be 1500 degrees C or less.
- the heat-resistant particles have electrical insulation properties, are stable to solvents and electrolytes used in the production of the heat-resistant insulating layer, and are electrochemically stable that are not easily oxidized and reduced in the battery operating voltage range. It is preferable that The heat-resistant particles may be organic particles or inorganic particles, but are preferably inorganic particles from the viewpoint of stability.
- the heat-resistant particles are preferably fine particles from the viewpoint of dispersibility, and fine particles having an average secondary particle diameter (median diameter, D50) of, for example, 100 nm to 4 ⁇ m, preferably 300 nm to 3 ⁇ m, more preferably 500 nm to 3 ⁇ m. Is used.
- the average secondary particle diameter (median diameter) can be determined by a dynamic light scattering method.
- the shape of the heat-resistant particles is not particularly limited, and may be a nearly spherical shape, or may be a plate shape, a rod shape, or a needle shape.
- the inorganic particles (inorganic powder) having a melting point or thermal softening point of 150 ° C. or higher are not particularly limited.
- inorganic particles for example, iron oxide (FeO), SiO 2 , Al 2 O 3 , aluminosilicate (aluminosilicate), TiO 2 , BaTiO 2 , ZrO 2 and other inorganic oxides; aluminum nitride, silicon nitride Inorganic nitrides such as: Calcium fluoride, barium fluoride, barium sulfate and other insoluble ion crystals; Silicon, diamond and other covalently bonded crystals; and Montmorillonite clay and other particles.
- the inorganic oxide may be a mineral resource-derived substance such as boehmite, zeolite, apatite, kaolin, mullite, spinel, olivine, mica, or an artificial product thereof.
- the inorganic particles may be particles that are made electrically insulating by covering the surface of the conductive material with an electrically insulating material such as the above-described inorganic oxide.
- the conductive material metal; SnO 2, tin - conductive oxide such as indium oxide (ITO); carbon black, and the like can be exemplified carbonaceous material such as graphite.
- the inorganic oxide particles can be easily applied as a water-dispersed slurry on the resin porous substrate, and therefore, a separator can be produced by a simple method, which is preferable.
- alumina Al 2 O 3
- silica SiO 2
- aluminosilicate aluminosilicate
- Organic particles (organic powder) having a melting point or thermal softening point of 150 ° C. or higher include crosslinked polymethyl methacrylate, crosslinked polystyrene, crosslinked polydivinylbenzene, crosslinked styrene-divinylbenzene copolymer, polyimide, melamine resin, phenol Examples thereof include various crosslinked polymer particles such as resin and benzoguanamine-formaldehyde condensate.
- the organic particles include heat-resistant polymer particles such as polysulfone, polyacrylonitrile, polyaramid, polyacetal, and thermoplastic polyimide.
- the organic resin constituting these organic particles is a mixture of the above-exemplified materials, a modified body, a derivative, a copolymer (random copolymer, alternating copolymer, block copolymer, graft copolymer), It may be a crosslinked body (in the case of the above heat-resistant polymer fine particles).
- a copolymer random copolymer, alternating copolymer, block copolymer, graft copolymer
- it is desirable to use polymethyl methacrylate and polyaramid particles as organic particles.
- a separator mainly composed of a resin can be manufactured, and thus a light battery as a whole can be obtained.
- grains may be used individually by 1 type, and may be used in combination of 2 or more types.
- the thickness of the heat-resistant insulating layer constituted by using the heat-resistant particles is appropriately determined according to the type of battery, application, etc., and is not particularly limited.
- the thickness of the heat-resistant insulating layer for example, the total thickness of the heat-resistant insulating layers formed on both surfaces of the resin porous substrate is preferably about 5 to 200 ⁇ m.
- the total thickness of the heat-resistant insulating layers formed on both surfaces of the resin porous substrate is 5 to 200 ⁇ m, preferably 5 to 20 ⁇ m. More preferably, it is 6 to 10 ⁇ m.
- the thickness of the heat-resistant insulating layer is in such a range, high output performance can be secured while increasing the mechanical strength in the thickness direction (stacking direction).
- the thickness ratio A ′ / A ′′ of the heat-resistant insulating layer formed on both surfaces of the resin porous substrate may be set so as to satisfy the formula (1), but is preferably 1.2 or less, More preferably, it is 1.1 or less, that is, the thickness ratio A ′ / A ′′ of the heat-resistant insulating layer is preferably 1.0 to 1.2, more preferably 1.0 to 1.1. More preferred.
- the thicknesses of the heat-resistant insulating layers formed on both surfaces of the resin porous substrate are preferably the same as much as possible. Thereby, the two heat-resistant insulating layers can evenly hold both surfaces of the resin porous substrate, and curling of the separator can be suppressed.
- the porosity of the heat-resistant insulating layer composed of the heat-resistant particles is not particularly limited, but is preferably 40% or more, more preferably 50% or more from the viewpoint of ion conductivity. Moreover, if the porosity is 40% or more, the retainability of the electrolyte (electrolytic solution, electrolyte gel) is improved, and a high-power battery can be obtained.
- the porosity of the heat-resistant insulating layer is preferably 70% or less, more preferably 60% or less. When the porosity of the heat-resistant insulating layer is 70% or less, sufficient mechanical strength is obtained, and the effect of preventing a short circuit due to foreign matter is high.
- the content of the heat-resistant particles in the heat-resistant insulating layer is preferably 90 to 100% by mass, and more preferably 95 to 100% by mass.
- the two heat-resistant insulating layers can uniformly hold both surfaces of the porous resin substrate.
- the manufacturing method of the separator of this embodiment is not particularly limited. However, as a manufacturing method, for example, a slurry-like composition for a heat-resistant insulating layer containing heat-resistant particles having a melting point or a heat softening point of 150 ° C. or higher is applied on both surfaces of a resin porous substrate, and then dried. The method is used.
- the heat-resistant insulating layer composition is obtained by dispersing heat-resistant particles in a solvent, and may further contain an organic binder or the like as necessary.
- organic binder for enhancing the shape stability of the heat resistant insulating layer include carboxymethyl cellulose, hydroxyethyl cellulose, polyvinyl alcohol, polyvinyl butyral, polyvinyl pyrrolidone, and the like.
- the amount of the organic binder used is preferably 10% by mass or less, more preferably 5% by mass or less, with respect to the total mass of the heat-resistant particles and the organic binder.
- the solvent is not particularly limited as long as it can uniformly disperse the heat-resistant particles.
- examples of the solvent include water; aromatic hydrocarbons such as toluene; furans such as tetrahydrofuran; ketones such as methyl ethyl ketone, methyl isobutyl ketone and acetone; N-methylpyrrolidone; dimethylacetamide; dimethylformamide; Examples include ethyl acetate.
- ethylene glycol, propylene glycol, monomethyl acetate, or the like may be appropriately added to these solvents.
- a heat-resistant insulating layer can be easily produced by preparing an aqueous dispersion slurry using water as a solvent. Further, the composition for a heat-resistant insulating layer is preferably prepared so that the solid content concentration is 30 to 60% by mass.
- Basis weight at the time of applying the resin porous substrate in heat insulating layer composition is not particularly limited, preferably 5 ⁇ 20g / m 2, more preferably from 9 ⁇ 13g / m 2.
- “weight” refers to the weight (g / m 2 ) of the heat-resistant insulating layer composition per unit area of the resin porous substrate. If it is the said range, the heat resistant insulating layer which has a suitable porosity and thickness will be obtained.
- the coating method is not particularly limited, and examples thereof include a knife coater method, a gravure coater method, a screen printing method, a Mayer bar method, a die coater method, a reverse roll coater method, an ink jet method, a spray method, and a roll coater method.
- the method of drying the heat-resistant insulating layer composition after coating is not particularly limited, and for example, a method such as warm air drying is used.
- the drying temperature is, for example, 30 to 80 ° C.
- the drying time is, for example, 2 seconds to 50 hours.
- the total thickness of the separator thus obtained is not particularly limited, but it can be generally used if it is about 5 to 30 ⁇ m. In order to obtain a compact battery, it is preferable to make it as thin as possible within a range in which the function as the electrolyte layer can be secured. Therefore, in order to contribute to the improvement of battery output by reducing the thickness, the total thickness of the separator is preferably 20 to 30 ⁇ m, more preferably 20 to 25 ⁇ m.
- the electrolyte layer is not particularly limited as long as it is formed using the separator of the present embodiment. That is, the electrolyte layer of the present embodiment has the separator, and an electrolyte contained in the separator porous resin substrate and the heat-resistant insulating layer. Moreover, it is preferable that the electrolyte hold
- the electrolyte layer a separator containing an electrolytic solution having excellent ion conductivity can be used. Further, an electrolyte layer formed by impregnating, applying, spraying, etc. a gel electrolyte or the like into a separator can also be used.
- the electrolytes include LiClO 4 , LiAsF 6 , LiPF 5 , LiBOB, LiCF 3 SO 3 and Li (CF 3 SO 2 ) 2. At least one of N can be used.
- the solvent for the electrolyte examples include ethylene carbonate (EC), propylene carbonate, diethyl carbonate (DEC), dimethyl carbonate, methyl ethyl carbonate, 1,2-dimethoxyethane, 1,2-diethoxyethane, tetrahydrofuran, 1, At least one kind selected from ethers composed of 3-dioxolane and ⁇ -butyllactone can be used. It is preferable to use an electrolytic solution in which the electrolyte is dissolved in the solvent and the concentration of the electrolyte is adjusted to 0.5 to 2M. However, the present invention is not limited to these.
- the amount of the electrolytic solution retained in the separator by impregnation or the like may be impregnated or applied to the separator's liquid retention capacity range, but may be impregnated beyond the liquid retention capacity range. This is because, for example, in the case of a bipolar battery, a resin can be injected into the electrolyte seal portion to prevent the electrolyte solution from exuding from the electrolyte layer, so that it can be impregnated as long as it can be retained in the separator of the electrolyte layer. is there.
- the battery element can be enclosed in the battery exterior material to prevent the electrolyte from leaking out from the inside of the battery exterior material, impregnation is performed as long as the liquid can be retained inside the battery exterior material. Is possible.
- the electrolytic solution can be impregnated in the separator by a conventionally known method such as completely sealing after injecting by a vacuum injection method or the like.
- (B) Gel electrolyte layer The gel electrolyte layer of the present invention is obtained by impregnating and applying the gel electrolyte to the separator of the present embodiment.
- the gel electrolyte has a configuration in which the above liquid electrolyte (electrolytic solution) is injected into a matrix polymer made of an ion conductive polymer.
- the ion conductive polymer used as the matrix polymer include polyethylene oxide (PEO), polypropylene oxide (PPO), and copolymers thereof.
- PEO polyethylene oxide
- PPO polypropylene oxide
- copolymers thereof in such a polyalkylene oxide polymer, an electrolyte salt such as a lithium salt can be well dissolved.
- the ratio of the liquid electrolyte (electrolytic solution) in the gel electrolyte is not particularly limited, but is preferably about several mass% to 98 mass% from the viewpoint of ionic conductivity.
- the gel electrolyte having a large amount of electrolytic solution having a ratio of the electrolytic solution of 70% by mass or more is particularly effective.
- the gel electrolyte matrix polymer can exhibit excellent mechanical strength by forming a crosslinked structure.
- a polymerization treatment may be performed on a polymerizable polymer for forming a polymer electrolyte using an appropriate polymerization initiator.
- the polymerization treatment include thermal polymerization, ultraviolet polymerization, radiation polymerization, and electron beam polymerization.
- PEO or PPO can be used as the polymerizable polymer.
- the thickness of the electrolyte layer is not particularly limited, but is basically about the same as or slightly thicker than the thickness of the separator of this embodiment. If the thickness of the electrolyte layer is usually about 5 to 30 ⁇ m, it can be used.
- the electrolyte of the electrolyte layer may contain various conventionally known additives as long as the effects of the present invention are not impaired.
- a current collecting plate may be used for the purpose of extracting the current outside the battery.
- the current collector plate is electrically connected to the current collector and the lead, and is taken out of the laminate sheet that is a battery exterior material.
- the material constituting the current collector plate is not particularly limited, and a known highly conductive material can be used as a current collector plate for a lithium ion secondary battery.
- a constituent material of the current collector plate for example, metal materials such as aluminum, copper, titanium, nickel, stainless steel (SUS), and alloys thereof are preferable.
- As a constituent material of the current collector plate aluminum, copper, and the like are particularly preferable from the viewpoint of light weight, corrosion resistance, and high conductivity.
- the same material may be used for a positive electrode current collecting plate and a negative electrode current collecting plate, and a different material may be used.
- ⁇ Use positive terminal lead and negative terminal lead as required.
- a terminal lead used in a known lithium ion secondary battery can be used.
- battery exterior materials As the battery exterior material 29, a known metal can case can be used. Moreover, as the battery exterior material 29, a bag-like case using a laminate film containing aluminum that can cover the power generation element can be used. As the laminate film, for example, a film having a three-layer structure in which PP, aluminum, and nylon are laminated in this order can be used, but is not limited thereto. A laminate film is desirable from the viewpoint that it is excellent in high output and cooling performance, and can be suitably used for a battery for large equipment for EV and HEV.
- said lithium ion secondary battery can be manufactured with a conventionally well-known manufacturing method.
- FIG. 4 is a perspective view showing the appearance of a flat plate type lithium ion secondary battery.
- the stacked battery 10 has a rectangular flat shape, and a positive electrode current collector plate 25 and a negative electrode current collector plate 27 for taking out electric power are drawn out from both sides thereof. Yes.
- the power generation element 21 is wrapped by the battery outer material 29 of the stacked battery 10, and the periphery of the battery outer material 29 is heat-sealed.
- the power generation element 21 is sealed with the positive electrode current collector plate 25 and the negative electrode current collector plate 27 pulled out to the outside.
- the power generation element 21 is formed by laminating a plurality of single battery layers (single cells) 19 including a positive electrode (positive electrode active material layer 13), an electrolyte layer 17 and a negative electrode (negative electrode active material layer 15) shown in FIG. .
- the drawing of the positive electrode current collector plate 25 and the negative electrode current collector plate from the battery exterior material 29 shown in FIG. 4 is not particularly limited.
- the positive electrode current collector plate 25 and the negative electrode current collector plate 27 may be drawn from the same side.
- the positive electrode current collector plate 25 and the negative electrode current collector plate 27 may be divided into a plurality of parts and taken out from each side. That is, the extraction of the positive electrode current collector plate 25 and the negative electrode current collector plate from the battery exterior material 29 is not limited to that shown in FIG.
- a lithium ion secondary battery is exemplified as the electric device.
- the present invention is not limited to this, and can be applied to other types of secondary batteries and further to primary batteries. Moreover, it can be applied not only to batteries but also to capacitors.
- Example 1 An aqueous dispersion of aluminosilicate fine particles, which is a composition for a heat-resistant insulating layer, was applied to both surfaces of a polyethylene (PE) microporous film, which is a resin porous substrate, using a blade coater.
- PE polyethylene
- the polyethylene microporous membrane has a thickness of 18.9 ⁇ m and a porosity of 42%.
- the aluminosilicate fine particles have an average secondary particle diameter of 1 ⁇ m and a melting point of 1000 ° C. or higher.
- the solid content concentration of the aqueous dispersion of aluminosilicate fine particles is 40% by mass.
- This separator with a heat-resistant insulating layer was formed in a roll shape having a width of 200 mm.
- the heat-resistant insulating layer was coated so that the thickness on one side was 2.8 ⁇ m or more, but finished with a thick side of 3.1 ⁇ m and a thin side of 2.5 ⁇ m.
- the obtained separator with a heat-resistant insulating layer had a total thickness of 24.5 ⁇ m, and the porosity of the heat-resistant insulating layer was 47%.
- Examples 2 to 12 Comparative Examples 1 to 4
- a separator having a porous resin substrate and a heat-resistant insulating layer shown in Table 1 was produced.
- Examples 2, 3, 6 and 11 and Comparative Example 2 a polypropylene (PP) microporous film (porosity 55%) was used as the resin porous substrate instead of the polyethylene microporous film.
- PP polypropylene
- Example 8 a non-woven fabric made of polyethylene terephthalate (PET) was used as the resin porous substrate instead of the polyethylene microporous membrane.
- the nonwoven fabric made of polyethylene terephthalate has a film thickness of 11.1 ⁇ m and a porosity of 48%.
- Comparative Examples 1, 4 and 5 a polyethylene (PE) microporous film (porosity 42%) was used as the resin porous substrate.
- PE polyethylene
- Examples 2 to 7, Examples 10 and 11, and Comparative Examples 2 and 3 high-purity alumina particles were used as the heat-resistant particles instead of the aluminosilicate of Example 1.
- the high purity alumina particles have an average secondary particle diameter of 1.5 ⁇ m and a melting point of 1000 ° C. or higher.
- Example 8 a methyl ethyl ketone dispersion of colloidal silica particles was used in place of the aluminosilicate aqueous dispersion of Example 1.
- the colloidal silica particles have an average secondary particle diameter of 0.4 ⁇ m and a melting point of 1000 ° C. or higher.
- the methyl ethyl ketone dispersion has a solid content concentration of 30% by mass.
- Example 9 instead of the aluminosilicate aqueous dispersion of Example 1, crosslinked polymethyl acrylate particles were used.
- the crosslinked polymethyl acrylate particles have an average secondary particle diameter of 1 ⁇ m and a heat softening point of about 160 ° C.
- Example 12 an NMP dispersion of an aromatic polyamide (aramid) resin was used as the heat-resistant insulating layer composition, and ethylene glycol was added to form a porous layer.
- aromatic polyamide (aramid) resin was used as the heat-resistant insulating layer composition, and ethylene glycol was added to form a porous layer.
- Example 5 A separator was produced in the same manner as in Example 1 except that the heat-resistant insulating layer was applied to one side of the resin porous substrate.
- the curl height of the separator produced in each example and comparative example was measured by the following procedure. First, as shown in FIG. 5, the separator was cut out from the separator roll so as to be substantially square, placed on a horizontal plane, and then static electricity was removed by stroking with a static elimination brush twice. Thereafter, the heights of the eight positions A to H in FIG. 5 that were lifted from the horizontal plane in 60 seconds were measured, and the maximum value was taken as the curl height (mm). When it was rolled up, it was unwound and stretched upward, and its height was taken as the measured value.
- Aluminum foil was prepared as a positive electrode current collector, and copper foil was prepared as a negative electrode current collector.
- a positive electrode active material slurry was prepared using lithium cobalt nickel manganate (LiNi 0.33 Co 0.33 Mn 0.33 O 2 ) as the positive electrode active material.
- a negative electrode active material slurry was prepared using artificial graphite as the negative electrode active material. The positive electrode active material slurry and the negative electrode active material slurry were applied to an aluminum foil as a positive electrode current collector and a copper foil as a negative electrode current collector, respectively, dried, and then roll pressed to produce a positive electrode and a negative electrode.
- the separator prepared in each Example and Comparative Example was sandwiched between the positive electrode and the negative electrode prepared above, a non-aqueous electrolyte was injected, and sealed in a laminate sheet to prepare an evaluation battery.
- the first charge / discharge was performed and the battery capacity was measured.
- the initial discharge capacity was 20 mAh.
- the discharge capacity at 4.0 mA and the discharge capacity at 50 mA were measured, and the ratio (discharge capacity at 50 mA / discharge capacity at 4.0 mA) was determined as a rate characteristic (rate ratio) ( %).
- Table 1 shows the results of rate characteristics of the examples and comparative examples.
- FIG. 6 shows the relationship between the parameter X and the curl height
- FIG. 7 shows the relationship between the parameter Y and the curl height and rate characteristics.
- the separators produced in Examples 1 to 12 had a parameter X value of 0.15 or more.
- the curl height was 5 mm or less, and there was no problem even when the plates were laminated by a flat plate continuous laminator, and good products were obtained continuously.
- the processes including cutting with a hot blade, conveyance with a porous adsorption pad, and lamination with a four-point clamp are repeated several tens of times, and the end portions are laminated without being folded. It was confirmed.
- stacking by a 4-point clamp was performed in about 3 seconds.
- the parameter Y was 0.3 to 0.7, and a sufficient output exceeding 85% was obtained.
- the rate characteristics are less than 85%, and the product performance is slightly insufficient.
- the balance of shrinkage stress of the heat-resistant insulating layers on both sides is improved by controlling the thickness and the total thickness of the heat-resistant insulating layers on both sides. Further, the balance between the internal stress of the resin porous substrate and the shrinkage stress of the heat-resistant insulating layer is improved. For this reason, curling is unlikely to occur during lamination, and a highly reliable electric device can be stably manufactured.
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Abstract
Description
図1では、本発明の一実施形態である、平板積層型(扁平型)のリチウムイオン二次電池の全体構造を示す。なお、平板積層型のリチウムイオン二次電池を、単に「積層型電池」ともいう。 [Battery overall structure]
FIG. 1 shows an overall structure of a flat plate type (flat type) lithium ion secondary battery according to an embodiment of the present invention. Note that a flat plate type lithium ion secondary battery is also simply referred to as a “stacked battery”.
正極活物質層13及び負極活物質層15は活物質を含み、必要に応じてその他の添加剤をさらに含む。 [Active material layer]
The positive electrode
正極集電体11及び負極集電体12は、導電性材料から構成される。集電体の大きさは、電池の使用用途に応じて決定される。例えば、高エネルギー密度が要求される大型の電池の場合は、面積の大きな集電体が用いられる。本実施形態のリチウムイオン電池は、好ましくは大型の電池であり、用いられる集電体の大きさは、例えば長辺が100mm以上であり、好ましくは100mm×100mm以上であり、より好ましくは200mm×200mm以上である。集電体の厚さについても特に制限はない。集電体の厚さは、通常は1~100μm程度である。集電体の形状についても特に制限されない。図1に示す積層型電池10では、集電箔のほか、網目形状(エキスパンドグリッド等)等を用いることができる。 [Current collector]
The positive electrode
電解質層17は、本実施形態のセパレータの面方向中央部に、電解質が保持されている構成を有する。本実施形態のセパレータを用いることで、積層時における端部のカールの発生を抑制することができるため、信頼性の高い電池を安定的に製造することができる。 [Electrolyte layer]
The
本実施形態における耐熱絶縁層付セパレータは、樹脂多孔質基体と、樹脂多孔質基体の両面に形成された、融点又は熱軟化点が150℃以上である耐熱粒子を含む耐熱絶縁層とを備える。さらに、前記セパレータは、下記数式(1)で表されるパラメータXが0.15以上であることを特徴とする。 (Separator with heat-resistant insulating layer)
The separator with a heat-resistant insulating layer in the present embodiment includes a resin porous substrate and a heat-resistant insulating layer containing heat-resistant particles having a melting point or a heat softening point of 150 ° C. or higher formed on both surfaces of the resin porous substrate. Further, the separator is characterized in that a parameter X represented by the following mathematical formula (1) is 0.15 or more.
樹脂多孔質基体2としては、例えば、電解質を吸収保持する有機樹脂を含む多孔性シート、織布又は不織布を挙げることができる。樹脂多孔質基体に含まれる有機樹脂としては、ポリエチレン(PE)、ポリプロピレン(PP)などのポリオレフィン;ポリイミド、アラミド;ポリエチレンテレフタレート(PET)などのポリエステルを用いることが好ましい。また、樹脂多孔質基体に形成されている細孔の孔径の平均値(平均細孔径)は、10nm~1μmであることが好ましい。なお、樹脂多孔質基体に形成されている細孔径は、例えば、窒素ガス吸着法により求めることができる。また、樹脂多孔質基体の厚さは、1μm~200μmであることが好ましい。さらに、樹脂多孔質基体の空隙率は20~90%であることが望ましい。 (Resin porous substrate)
Examples of the resin
本実施形態では、耐熱絶縁層を構成する耐熱粒子の材質としては、融点又は熱軟化点が150℃以上、好ましくは240℃以上である、耐熱性の高いものを用いる。このような耐熱性の高い材質を用いることで、電池内部温度が200℃前後に達してもセパレータの収縮を有効に防止することができる。その結果、電極間のショートの誘発を防ぐことができるため、温度上昇による性能低下が起こりにくい電池を得ることができる。なお、本明細書において、「熱軟化点」とは、加熱された物質が軟化し、変形し始める温度をいい、ビカット軟化温度のことをいう。なお、耐熱粒子の融点又は熱軟化点の上限は特に限定されないが、例えば1500℃以下とすることができる。 (Heat-resistant insulating layer (heat-resistant insulating porous layer))
In this embodiment, as the material of the heat resistant particles constituting the heat resistant insulating layer, a material having a high heat resistance having a melting point or a heat softening point of 150 ° C. or higher, preferably 240 ° C. or higher is used. By using such a material having high heat resistance, it is possible to effectively prevent the separator from contracting even when the battery internal temperature reaches around 200 ° C. As a result, it is possible to prevent induction of a short circuit between the electrodes, and thus it is possible to obtain a battery in which performance deterioration due to temperature rise hardly occurs. In the present specification, the “thermal softening point” refers to a temperature at which a heated substance softens and begins to deform, and refers to a Vicat softening temperature. In addition, although the upper limit of melting | fusing point or heat softening point of a heat-resistant particle | grain is not specifically limited, For example, it can be 1500 degrees C or less.
本実施形態のセパレータの製造方法は特に制限されない。ただ、製造方法としては、例えば、樹脂多孔質基体の両面に、融点又は熱軟化点が150℃以上である耐熱粒子を含有する、スラリー状の耐熱絶縁層用組成物を塗布した後、乾燥する方法が用いられる。 (Manufacturing method of separator)
The manufacturing method of the separator of this embodiment is not particularly limited. However, as a manufacturing method, for example, a slurry-like composition for a heat-resistant insulating layer containing heat-resistant particles having a melting point or a heat softening point of 150 ° C. or higher is applied on both surfaces of a resin porous substrate, and then dried. The method is used.
本実施形態のセパレータに染み込ませることができる電解液において、電解質としては、LiClO4、LiAsF6、LiPF5、LiBOB、LiCF3SO3及びLi(CF3SO2)2Nの少なくとも1種類を用いることができる。また、電解液の溶媒としては、エチレンカーボネート(EC)、プロピレンカーボネート、ジエチルカーボネート(DEC)、ジメチルカーボネート、メチルエチルカーボネート、1,2-ジメトキシエタン、1,2-ジエトキシエタン、テトラヒドロフラン、1,3-ジオキソラン及びγ-ブチルラクトンよりなるエーテル類から少なくとも1種類を用いることができる。そして、前記電解質を前記溶媒に溶解させ、電解質の濃度を0.5~2Mに調整した電解液を使用することが好ましい。ただ、本発明はこれらに制限されない。 (A) Electrolyte-containing separator In the electrolyte solution that can be infiltrated into the separator of this embodiment, the electrolytes include LiClO 4 , LiAsF 6 , LiPF 5 , LiBOB, LiCF 3 SO 3 and Li (CF 3 SO 2 ) 2. At least one of N can be used. Examples of the solvent for the electrolyte include ethylene carbonate (EC), propylene carbonate, diethyl carbonate (DEC), dimethyl carbonate, methyl ethyl carbonate, 1,2-dimethoxyethane, 1,2-diethoxyethane, tetrahydrofuran, 1, At least one kind selected from ethers composed of 3-dioxolane and γ-butyllactone can be used. It is preferable to use an electrolytic solution in which the electrolyte is dissolved in the solvent and the concentration of the electrolyte is adjusted to 0.5 to 2M. However, the present invention is not limited to these.
本発明のゲル電解質層は、本実施形態のセパレータにゲル電解質を含浸、塗布などにより保持させたものである。 (B) Gel electrolyte layer The gel electrolyte layer of the present invention is obtained by impregnating and applying the gel electrolyte to the separator of the present embodiment.
電池外部に電流を取り出す目的で、集電板を用いても良い。集電板は集電体やリードに電気的に接続され、電池外装材であるラミネートシートの外部に取り出される。 [Current collector and lead]
A current collecting plate may be used for the purpose of extracting the current outside the battery. The current collector plate is electrically connected to the current collector and the lead, and is taken out of the laminate sheet that is a battery exterior material.
電池外装材29としては、公知の金属缶ケースを用いることができる。また、電池外装材29としては、発電要素を覆うことができる、アルミニウムを含むラミネートフィルムを用いた袋状のケースを用いることができる。ラミネートフィルムとしては、例えば、PP、アルミニウム、ナイロンをこの順に積層してなる3層構造のフィルム等を用いることができるが、これらに制限されない。高出力化や冷却性能に優れ、EV、HEV用の大型機器用電池に好適に利用することができるという観点から、ラミネートフィルムが望ましい。 [Battery exterior materials]
As the
図4は、平板積層型リチウムイオン二次電池の外観を表した斜視図である。 [Appearance structure of lithium ion secondary battery]
FIG. 4 is a perspective view showing the appearance of a flat plate type lithium ion secondary battery.
樹脂多孔質基体であるポリエチレン(PE)微多孔膜の両面に、耐熱絶縁層用組成物であるアルミノシリケート微粒子の水分散体を、ブレードコータにより塗布した。ここで、ポリエチレン微多孔膜は、膜厚が18.9μmであり、空隙率が42%である。また、アルミノシリケート微粒子は、平均二次粒子径が1μmであり、融点が1000℃以上である。さらに、アルミノシリケート微粒子の水分散体の固形分濃度は40質量%である。その後、温風乾燥して耐熱絶縁層を形成し、耐熱絶縁層付セパレータを作製した。この耐熱絶縁層付セパレータは、幅200mmで、ロール状に形成した。 [Example 1]
An aqueous dispersion of aluminosilicate fine particles, which is a composition for a heat-resistant insulating layer, was applied to both surfaces of a polyethylene (PE) microporous film, which is a resin porous substrate, using a blade coater. Here, the polyethylene microporous membrane has a thickness of 18.9 μm and a porosity of 42%. The aluminosilicate fine particles have an average secondary particle diameter of 1 μm and a melting point of 1000 ° C. or higher. Furthermore, the solid content concentration of the aqueous dispersion of aluminosilicate fine particles is 40% by mass. Then, it dried with warm air, formed the heat-resistant insulating layer, and produced the separator with a heat-resistant insulating layer. This separator with a heat-resistant insulating layer was formed in a roll shape having a width of 200 mm.
実施例1と同様に、表1に示す樹脂多孔質基体、耐熱絶縁層を有するセパレータを作製した。 [Examples 2 to 12, Comparative Examples 1 to 4]
In the same manner as in Example 1, a separator having a porous resin substrate and a heat-resistant insulating layer shown in Table 1 was produced.
耐熱絶縁層を樹脂多孔質基体の片面に塗布したことを除いては、実施例1と同様にしてセパレータを作製した。 [Comparative Example 5]
A separator was produced in the same manner as in Example 1 except that the heat-resistant insulating layer was applied to one side of the resin porous substrate.
各実施例及び比較例で作製したセパレータのカール高さを以下の手順で測定した。まず、図5に示すように、セパレータのロールから、セパレータを略正方形となるように切り出し、水平面に載置した後、除電ブラシにて2度なでて静電気を除去した。その後、図5のA~Hの8箇所について、60秒間で水平面から浮き上がった高さを測定し、その最大値をカール高さ(mm)とした。丸く巻きこんだ場合には、巻いた部分をほどいて上方に伸ばし、その高さを測定値とした。 [Curl height]
The curl height of the separator produced in each example and comparative example was measured by the following procedure. First, as shown in FIG. 5, the separator was cut out from the separator roll so as to be substantially square, placed on a horizontal plane, and then static electricity was removed by stroking with a static elimination brush twice. Thereafter, the heights of the eight positions A to H in FIG. 5 that were lifted from the horizontal plane in 60 seconds were measured, and the maximum value was taken as the curl height (mm). When it was rolled up, it was unwound and stretched upward, and its height was taken as the measured value.
正極集電体としてアルミニウム箔を、負極集電体として銅箔をそれぞれ準備した。正極活物質としてコバルトニッケルマンガン酸リチウム(LiNi0.33Co0.33Mn0.33O2)を用いて正極活物質スラリーを調製した。一方、負極活物質として人造黒鉛を用いて負極活物質スラリーを調製した。正極活物質スラリー及び負極活物質スラリーを、それぞれ正極集電体であるアルミ箔及び負極集電体である銅箔に塗工し、乾燥させた後ロールプレスして正極及び負極を作製した。上記で作製した正極、負極の間に各実施例、比較例で作製したセパレータを挟み、非水電解液を注入し、ラミネートシート内に封止して評価用電池を作製した。なお、非水電解液としては、エチレンカーボネート:エチルメチルカーボネート=1:2(体積比)の混合溶媒に、溶質としてLiPF6を濃度1.0ml/Lとなるように溶解させたものを使用した [Battery evaluation]
Aluminum foil was prepared as a positive electrode current collector, and copper foil was prepared as a negative electrode current collector. A positive electrode active material slurry was prepared using lithium cobalt nickel manganate (LiNi 0.33 Co 0.33 Mn 0.33 O 2 ) as the positive electrode active material. On the other hand, a negative electrode active material slurry was prepared using artificial graphite as the negative electrode active material. The positive electrode active material slurry and the negative electrode active material slurry were applied to an aluminum foil as a positive electrode current collector and a copper foil as a negative electrode current collector, respectively, dried, and then roll pressed to produce a positive electrode and a negative electrode. The separator prepared in each Example and Comparative Example was sandwiched between the positive electrode and the negative electrode prepared above, a non-aqueous electrolyte was injected, and sealed in a laminate sheet to prepare an evaluation battery. As the non-aqueous electrolyte, a solution obtained by dissolving LiPF 6 as a solute at a concentration of 1.0 ml / L in a mixed solvent of ethylene carbonate: ethyl methyl carbonate = 1: 2 (volume ratio) was used.
2 樹脂多孔質基体
3 耐熱絶縁層
4 正極
5 負極
10 積層型電池(リチウムイオン二次電池)
11 正極集電体
12 負極集電体
13 正極活物質層
15 負極活物質層
17 電解質層
19 単電池層
21 発電要素
25 正極集電板
27 負極集電板
29 電池外装材(ラミネートフィルム) 1 Separator with heat-resistant insulating layer (separator)
2 Resin
DESCRIPTION OF
Claims (9)
- 樹脂多孔質基体と、
前記樹脂多孔質基体の両面に形成され、融点又は熱軟化点が150℃以上である耐熱粒子を含む耐熱絶縁層と、
を備え、
数式1で表されるパラメータXが、0.15以上であることを特徴とする電気デバイス用の耐熱絶縁層付セパレータ:
式中、A’及びA”は前記樹脂多孔質基体の両面に形成された各耐熱絶縁層の厚み(μm)であり、この際、A’≧A”であり、Cは前記耐熱絶縁層付セパレータの総厚み(μm)である。 A porous resin substrate;
A heat-resistant insulating layer comprising heat-resistant particles formed on both surfaces of the resin porous substrate and having a melting point or thermal softening point of 150 ° C. or higher;
With
The parameter X represented by Formula 1 is 0.15 or more, and a separator with a heat-resistant insulating layer for an electrical device:
In the formula, A ′ and A ″ are the thicknesses (μm) of the respective heat-resistant insulating layers formed on both surfaces of the porous resin substrate, where A ′ ≧ A ″, and C is with the heat-resistant insulating layer. This is the total thickness (μm) of the separator. - 数式2で表されるパラメータYが0.3~0.7の範囲であることを特徴とする請求項1に記載の耐熱絶縁層付セパレータ:
式中、Dは耐熱絶縁層の空隙率(%)である。 2. The separator with a heat-resistant insulating layer according to claim 1, wherein the parameter Y represented by Formula 2 is in the range of 0.3 to 0.7:
In the formula, D is the porosity (%) of the heat-resistant insulating layer. - 前記パラメータXが、0.20以上であることを特徴とする請求項1又は2に記載の耐熱絶縁層付セパレータ。 The separator with heat-resistant insulating layer according to claim 1 or 2, wherein the parameter X is 0.20 or more.
- 前記耐熱粒子が、無機酸化物の粒子であることを特徴とする請求項1乃至3のいずれか一項に記載の耐熱絶縁層付セパレータ。 The separator with a heat-resistant insulating layer according to any one of claims 1 to 3, wherein the heat-resistant particles are inorganic oxide particles.
- 前記耐熱粒子が、有機樹脂の粒子であることを特徴とする請求項1乃至3のいずれか一項に記載の耐熱絶縁層付セパレータ。 4. The separator with a heat resistant insulating layer according to claim 1, wherein the heat resistant particles are organic resin particles. 5.
- 前記耐熱絶縁層の空隙率は、40~70%であることを特徴とする請求項1乃至5のいずれか一項に記載の耐熱絶縁層付セパレータ。 The separator with a heat-resistant insulating layer according to any one of claims 1 to 5, wherein a porosity of the heat-resistant insulating layer is 40 to 70%.
- 前記耐熱絶縁層の厚みの合計は5~200μmであり、前記耐熱絶縁層の厚みの比(A’/A”)は1.0~1.2であることを特徴とする請求項1乃至6のいずれか一項に記載の耐熱絶縁層付セパレータ。 The total thickness of the heat-resistant insulating layer is 5 to 200 μm, and the thickness ratio (A ′ / A ″) of the heat-resistant insulating layer is 1.0 to 1.2. The separator with a heat-resistant insulating layer according to any one of the above.
- 請求項1乃至7のいずれか一項に記載の耐熱絶縁層付セパレータと、
前記耐熱絶縁層付セパレータの樹脂多孔質基体及び耐熱絶縁層の内部に含有される電解質と、
を備えることを特徴とする電気デバイス用の電解質層。 A separator with a heat-resistant insulating layer according to any one of claims 1 to 7,
An electrolyte contained inside the resin porous substrate and the heat-resistant insulating layer of the separator with the heat-resistant insulating layer;
An electrolyte layer for an electrical device, comprising: - 請求項1乃至7のいずれか一項に記載の耐熱絶縁層付セパレータを備えることを特徴とする電気デバイス。 An electric device comprising the separator with a heat-resistant insulating layer according to any one of claims 1 to 7.
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US14/127,741 US9312527B2 (en) | 2011-06-22 | 2012-06-13 | Separator having heat resistant insulation layers |
MX2013014658A MX349899B (en) | 2011-06-22 | 2012-06-13 | Separator having heat resistant insulation layers. |
EP12802928.7A EP2725636B1 (en) | 2011-06-22 | 2012-06-13 | Separator having heat resistant insulation layers |
BR112013032308A BR112013032308A2 (en) | 2011-06-22 | 2012-06-13 | separator with heat resistant insulation layers |
KR1020147001329A KR101639923B1 (en) | 2011-06-22 | 2012-06-13 | Separator having heat resistant insulation layers |
RU2014101718/07A RU2562970C2 (en) | 2011-06-22 | 2012-06-13 | Separator having heat-resistant insulating layers |
CN201280028947.2A CN103608948B (en) | 2011-06-22 | 2012-06-13 | With the dividing plate of heat-resistant insulating layer |
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Also Published As
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RU2562970C2 (en) | 2015-09-10 |
KR101639923B1 (en) | 2016-07-14 |
EP2725636A4 (en) | 2014-12-31 |
US20140113176A1 (en) | 2014-04-24 |
CN103608948B (en) | 2016-04-13 |
RU2014101718A (en) | 2015-08-10 |
EP2725636B1 (en) | 2017-08-09 |
TW201301635A (en) | 2013-01-01 |
MY161020A (en) | 2017-03-31 |
MX349899B (en) | 2017-08-18 |
JP2013008481A (en) | 2013-01-10 |
JP5796367B2 (en) | 2015-10-21 |
EP2725636A1 (en) | 2014-04-30 |
TWI466365B (en) | 2014-12-21 |
US9312527B2 (en) | 2016-04-12 |
BR112013032308A2 (en) | 2016-12-20 |
MX2013014658A (en) | 2014-03-27 |
KR20140039305A (en) | 2014-04-01 |
CN103608948A (en) | 2014-02-26 |
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